1. Field of the Invention
The present invention relates to compositions and methods for dyeing keratin fibers, especially human hair, and, more particularly, to compositions for dyeing keratin fibers, especially human hair, containing nitrophenylamines.
2. Prior Art
Nitro dyes have achieved a significant importance, especially for dyeing hair. In oxidizing hair dye compositions, they are an important constituent for modifying the dyeing result and for achieving fashionable color nuances. However, by combining yellow, red and blue nitro dyes, dyeing agents can also be produced, which are able to color hair in natural to fashionable shades without the addition of oxidizing agents.
Of particular importance in this connection are yellow nitro dyes, which are taken up directly and dye the hair an intensive lemon yellow, which is to be as free as possible from red portions. Furthermore, nitro dyes must also fulfill a whole series of additional requirements. For example, they must be safe from a toxicological and dermatological point of view and must make it possible to obtain dyed colors of the desired intensity. Among other things, this assumes that they are sufficiently soluble in water. In addition, a good light fastness, rubbing fastness, permanent waving fastness and perspiration resistance is required for the colorings achieved. On the other hand, the dyes should not wash out too easily once again during a subsequent treatment or when the hair is washed. Their use in oxidizing hair dye compositions presupposes furthermore that they are stable in the presence of reducing agents and oxidizing agents and especially in alkaline solution.
It is an object of the present invention to provide improved dye compositions containing nitrophenylamines, which meet the requirements for dyeing fibers, especially human hair, in an outstanding manner.
It is another object of the present invention to provide improved methods for dyeing keratin fibers, especially human hair, which utilizes the improved dye compositions.
Surprisingly, it has now been found that certain 4-nitrophenylamines have good water solubility and make an intensively luminous, yellow coloration possible. In addition, they have outstanding light fastness, rubbing fastness, permanent waving fastness and perspiration resistance.
The present invention therefore relates to compositions for dyeing fibers, particularly keratin fibers, such as human hair. The dye compositions are characterized in that they contain at least one compound of formula (I) 
wherein, independently of one another
R1 represents hydrogen or a linear or branched alkyl group with 1 to 4 carbon atoms and
Y is a heterocyclic ring of formula (II) 
with X representing nitrogen or oxygen, m is 1, 2 or 3 and n is 0 or 1; or Y is an amino group NR2R3, and R2 and R3, independently of one another, each represent hydrogen, a cycloalkyl group with 1 to 6 carbon atoms or a xe2x80x94(CH2)OR4 group, in which z is 1, 2, 3, 4, 5 or 6 with R4 being a linear or branched alkyl group with 1 to 4 carbon atoms, with the proviso that R2 and R3 cannot simultaneously be hydrogen.
The compounds of the general formula (I) preferably are selected from N-(2-methoxyethyl)-4-nitrophenylamine, N-(2-methoxyethyl)-2-methyl-4-nitrophenylamine, 4-(4-nitrophenyl)morpholine, N-(3-methoxypropyl)-4-nitrophenylamine, N-(3-methoxypropyl)-2-methyl-4-nitrophenylamine, 4-(2-methyl-4-nitrophenyl)-morpholine, N-cyclopropyl-4-nitrophenylamine, 4-nitro-N-((tetrahydrofuran-2-yl)methyl)-phenylamine, 2-methyl-4-nitro-N-(tetrahydrofuran-2-yl-methyl)-phenylamine and N-cyclopropyl-2-methyl-4-nitrophenylamine.
The dyes of formula (I) are used in the inventive dye compositions preferably in a total amount of 0.01 to 10% by weight and particularly in a total amount of 0.1% to 5% by weight.
The dyes of formula (I) can easily be synthesized from available precursors and not only have a good water solubility, but also a very good absorption behavior from anionic, cationic, amphoteric or nonionic carrier compositions. The coloring obtained has a very high resistance towards being washed out and towards perspiration and light radiation, as well as towards bases, such as ammonia and acids, such as phosphoric acid or reducing agents, such as ascorbic acid or sodium sulfite, so that their use in oxidative dye compositions is facilitated appreciably. In addition, the inventive dye compositions have a good shelf life and make possible intensively luminous yellow color shades, with possibilities for varying them in all gradations and nuances from a bright lemon yellow to an intensive dark yellow.
The inventive dye compositions can be used with and also without the addition of an oxidizing agent. In the former case, the usual developing and coupling substances are added.
If the dye composition is used without an oxidizing agent, it may contain, aside from the dyes of formula (I), further, known direct-dyeing dyes from the group comprising nitro, azo, anthraquinone and triphenylmethane dyes, either alone or in admixture with one another.
Example of suitable dyes, which are picked up directly, are 1,4-bis[(2-hydroxyethyl)amino]-2-nitrobenzene, 1-(2-hydroxyethyl)amino-2-nitro-4-[di(2-hydroxyethyl)amino]-benzene (HC Blue No. 2), 1-amino-3-methyl-4-[(2-hydroxyethyl)amino]-6-nitrobenzene (HC Violet No. 1), 4-[ethyl-(2-hydroxyethyl)-amino]-1-[(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Blue No. 12), 4-[di-(2-hydroxyethyl)amino]-1-[(2-methoxyethyl)amino]-2-nitrobenzene (HC Blue No. 11), 1-[(2,3-dihydroxypropyl)amino]-4-[methyl-(2-hydroxyethyl)amino]-2-nitrobenzene (HC Blue No. 10), 1-[(2,3-dihydroxypropyl)amino]-4-[ethyl-(2-hydroxyethyl)amino-2-nitrobenzene hydrochloride (HC Blue No. 9), 1-(3-hydroxypropylamino)-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene (HC Violet No. 2), 1-methylamino-4-[methyl-(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Blue No. 6), 2-((4-amino-2-nitrophenyl)amino)-5-dimethylamino-benzoic acid (HC Blue No. 13), 1-amino-4-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Red No. 7), 2-amino-4,6-dinitrophenol, 4-amino-2-nitrodiphenylamine (HC Red No. 1), 1-amino-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Red No. 13), 1-amino-5-chloro-4-[(2-hydroxyethyl)amino]-2-nitrobenzene, 4-amino-1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitrophenol, 1-[(2-aminoethyl)amino]-4-(2-hydroxyethoxy)-2-nitrobenzene (HC Orange No. 2), 4-(2,3-dihydroxypropoxy)-1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Orange No. 3), 1-amino-5-chloro-4-[(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red No. 10), 5-chloro-1,4-[di(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red No. 11), 2-[(2-hydroxyethyl)amino]-4,6-dinitrophenol, 4-ethylamino-3-nitrobenzoic acid, 2-[(4-amino-2-nitrophenyl)amino]-benzoic acid, 2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 4-[(3-hydroxypropyl)amino]-3-nitrophenol, 2,5-diamino-6-nitropyridine, 1,2,3,4-tetrahydro-6-nitroquinoxaline, 7-amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazine (HC Red No. 14), 1-amino-2-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 5), 1-(2-hydroxyethoxy)-2-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 4), 1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Yellow No. 2), 2-[(2-hydroxyethyl)amino]-1-methoxy-5-nitrobenzene, 2-amino-3-nitrophenol, 1-(2-hydroxyethoxy)-3-methylamino-4-nitrobenzene, 2,3-(dihydroxypropoxy)-3-methylamino-4-nitrobenzene, 2-[(2-hydroxyethyl)amino]-5-nitrophenol (HC Yellow No. 11), 3-[(2-aminoethyl)amino]-1-methoxy-4-nitrobenzene hydrochloride (HC Yellow No. 9), 1-[(2-ureidoethyl)amino]-4-nitrobenzene, 4-[(2,3-dihydroxypropyl)amino]-3-nitro-1-fluoro-methylbenzene (HC Yellow No. 6), 1-chloro-2,4-bis[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 10), 4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene, 1-chloro-4-[(2-hydroxyethyl)amino]-3-nitrobenzene (HC Yellow No. 12), 4-[(2-hydroxyethyl)amino]-3-nitro-1-trifluoromethylbenzene (HC Yellow No. 13), 4-[(2-hydroxyethyl)amino]-3-nitrobenzonitrile (HC Yellow No. 14), 4-[(2-hydroxyethyl)amino]-3-nitro-benzamide (HC Yellow No. 15), 1,4-di[(2,3-dihydroxypropyl)amino]-9,10-anthraquinone, 1-[(2-hydroxyethyl)amino-4-methylamino-9,10-anthraquinone (CI61505; Disperse Blue No. 3), 2-[(2-aminoethyl)amino]-9,10-anthraquinone (HC Orange No., 5), 1-hydroxy-4-[(4-methyl-2-sulfophenyl)amino]-9,10-anthraquinone, 1-[(3-aminopropyl)amino]-4-methylamino-9,10-anthraquinone (HC Blue No. 8), 1-[(3-aminopropyl)amino]-9,10-anthraquinone (HC Red No. 8), 1,4-diamino-2-methoxy-9,10-anthraquinone (CI62015; Disperse Red No. 11, Solvent Violet No. 26), 1,4-dihydroxy-5,8-bis[(2-hydroxyethyl)amino]-9,10-anthraquinone (CI62500; Disperse Blue No. 7, Solvent Blue No. 69), 9-(dimethylamino)-benzo[a]phenoxazin-7-ium chloride (CI51175; Basic Blue No. 6), di[4-(diethylamino)phenyl][4-(ethylamino)naphthyl]carbenium chloride (CI42595; Basic Blue No. 7), 3,7-di(dimethylamino)phenothiazin-5-ium chloride (CI52015; Basic Blue No. 9), di[4-(dimethylamino)phenyl][4-(phenylamino)naphthyl]carbenium chloride (CI44045; Basic Blue No. 26), 2-[(4-(ethyl(2-hydroxyethyl)amino)phenyl)azo]-6-methoxy-3-methyl-benzothiazolium methyl sulfate (CI11154; Basic Blue No. 41), 8-amino-2-bromo-5-hydroxy-4-imino-6-[(3-(trimethylammonio)phenyl)amino]-1(4H)-naphthalenone chloride (CI56059; Basic Blue No. 99), bis[4-(dimethylamino)phenyl][4-(methylamino)phenyl]carbenium chloride (CI42535; Basic Violet No. 1), tris[4-(dimethylamino)phenyl]carbenium chloride (CI42555; Basic Violet No. 3), 2-[3,6-(diethylamino)dibenzopyranium-9-yl]-benzoic acid chloride (CI45170; Basic Violet No. 10), di-(4-aminophenyl)(4-amino-3-methylphenyl)carbenium chloride (CI42510; Basic Violet No. 14), 1,3-bis[(2,4-diamino-5-methylphenyl)azo]-3-methylbenzene (CI21010; Basic Brown No. 4), 1-[(4-aminophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (CI12250; Basic Brown No. 16), 1-[(4-amino-2-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (Basic Brown No. 17), 1-[(4-amino-3-nitrophenyl)-azo]-7-(trimethylammonio)-2-naphthol chloride (CI12251; Basic Brown No. 17), 3,7-diamino-2,8-dimethyl-5-phenylphenazinium chloride (CI50240; Basic Red No. 2), 1,4-dimethyl-5-[(4-(dimethylamino)phenyl)azo]-1,2,4-triazolium chloride (CI11055; Basic Red No., 22), 2-hydroxy-1-[(2-methoxyphenyl)azo]-7-(trimethylammonio)-naphthalene chloride (CI12245; Basic Red No. 76), 2-[2-((2,4-dimethoxyphenyl)amino)ethenyl]-1,3,3-trimethyl-3H-indol-1-ium chloride (CI48055; Basic Yellow No. 11). 3-methyl-1-phenyl-4-[(3-(trimethylammonio)phenyl) azo]-pyrazol-5-one chloride (CI12719; Basic Yellow No. 57), bis[4-(diethylamino)-phenyl]phenylcarbenium hydrogen sulfate (1:1) (CI42040); Basic Green No. 1), 1-[di(2-hydroxyethyl)amino]-3-methyl-4-[(4-nitrophenyl)azo]-benzene (CI11210, Disperse Red No. 17), 4-[(4-aminophenyl)azo]-1-[di(2-hydroxyethyl)amino]-3-methylbenzene (HC Yellow No. 7), disodium 2,6-diamino-3-[(pyridin-3-yl)azo]-pyridine, disodium 6-hydroxy-5-[(4-sulfophenyl)azo]-2-naphthalenesulfonate (CI15985; Food Yellow No. 3), disodium 2,4-dinitro-1-naphthol-7-sulfonate (CI10316; Acid Yellow No. 1; Food Yellow No. 1), 2-(indan-1,3-dion-2-yl) quinolinesulfonic acid (CI47005; Food Yellow No. 13; Acid Yellow No. 3), trisodium 5-hydroxy-1-(4-sulfophenyl)-4-[(4-sulfophenyl)azo]pyrazol-3-carboxylate (CI19140; Food Yellow No. 4; Acid Yellow No. 23), 9-(2-carboxyphenyl)-6-hydroxy-3H-xanthen-3-one (CI45350; Acid Yellow No. 73), sodium 5-[(2,4-dinotrophenyl)amino]-2-phenylamino-benzosulfonate (CI10385; Acid Orange No. 3), sodium 4-[(2,4-dihydroxyphenyl)azo]-benzosulfonate (CI14270; Acid Orange No. 6), sodium 4-[(2-hydroxynaphth-1-yl)azo]-benzosulfonate (CI15510; Acid Orange No. 7), sodium 4-[(2,4-dihydroxy-3-[(2,4-dimethylphenyl)azo]-phenyl) azo]-benzosulfonate (CI20170; Acid Orange No. 24), disodium 4-hydroxy-3-[(4-sulfonaphth-1-yl)azo]-1-naphthalene sulfonate (CI14720; Acid Red No. 14), trisodium 6-hydroxy-5-[(4-sulfonaphth-1-yl)azo]-2,4-naphthalene disulfonate (CI16255; Ponceau 4R; Acid Red No. 18), trisodium 3-hydroxy-4-[(4-sulfonaphth-1-yl)azo]-2,7-naphthalene disulfonate (CI16185; Acid Red No. 27), disodium 8-amino-1-hydroxy-2-(phenylazo)-3,6-naphthalene disulfonate (CI17200; Acid Red No. 33), disodium 5-(acetylamino)-4-hydroxy-3-[(2-methylphenyl)azo]-2,7-naphthalene disulfonate (CI18065; Acid Red No. 35), disodium 2-(3-hydroxy-2,4-5,7-tetraioddibenzopyran-6-on-9-yl)-benzoate (CI45430; Acid Red No. 51), sodium N-[6-(diethylamino)-9-(2,4-disulfophenyl)-3H-xanthen-3-yliden]-N-ethylethaneammonium hydroxide inner salt (CI45100; Acid Red No. 52), disodium 8-[(4-phenylazo)phenyl)azo]-7-naphthol-1,3-disulfonate (CI27290; Acid Red No. 73), disodium 2xe2x80x2,4xe2x80x2,5xe2x80x2,7xe2x80x2-tetrabromo-3xe2x80x2-6xe2x80x2-dihydroxyspiro[isobenzofuran-1(3H),9xe2x80x2-[9H]xanthen]-3-one (CI45380; Acid Red No. 87), disodium 2xe2x80x2,4xe2x80x2,5xe2x80x2,7xe2x80x2-tetrabromo-4,5,6,7-tetrachloro-3xe2x80x2,6xe2x80x2-dihydroxyspiro[isobenzofuran-1(3H),9xe2x80x2[9xanthen]-3-one (CI45410; Acid Red No. 92), disodium 3xe2x80x2,6xe2x80x2-dihydroxy-4xe2x80x2,5xe2x80x2-diiodospiro[isobenzofuran-1(3H),9xe2x80x2(9H)-xanthen]-3-one (CI45425; Acid Red No. 95), disodium (2-sulfophenyl)di[4-(ethyl((4-sulfophenyl)methyl)amino)-phenyl]-carbenium salt, betaine (CI42090); Acid Blue No. 9; FDandC Blue No. 1), sodium salt of 1,4-bis(2-sulfo-4-methylphenyl)amino-9,10-anthraquinone (CI 61570; Acid Green No. 25), monosodium internal salt of bis[4-(dimethylamino)phenyl]-(3,7-disulfo-2-hydroxynaphth-1-yl)carbenium (CI44090; Food Green No. 4; Acid Green No. 50), internal sodium salt of bis[4-(diethylamino)phenyl](2,4-disulfophenyl)carbenium (2:1) (CI42045; Food Blue No. 3; Acid Blue No. 1), internal calcium salt of bis[4-(dimethylamino)phenyl](5-hydroxy-2,4-disulfophenyl)carbenium (2:1) (CI42051; Acid Blue No. 3), sodium 1-amino-4-(cyclohexylamino)-9,10-anthraquinone-2-sulfonate (CI62045; Acid Blue No. 62), disodium 2-(1,3-dihydro-3-oxo-5-sulfo-2H-indol-2-ylidene)-2,3-dihydro-3-oxo-1H-indole-5-sulfonate (CI73015; Acid Blue No. 74), internal monosodium salt of 9-(2-carboxyphenyl)-3-[(2-methylphenyl)amino]-6-[(2-methyl-4sulfophenyl) amino]xanthylium (CI45190; Acid Violet No. 9), sodium salt of 1-hydroxy-4-[(methyl-2-sulfophenyl)-amino]-9,10-anthraquinone (CI60730; DandC Violet No. 2; Acid Violet No. 43), bis[3-nitro-4-[(4-phenylamino)3-sulfophenylamino]-phenyl]sulfone (CI10410; Acid Brown No. 13), disodium 5-amino-4-hydroxy-6-[(4-nitrophenyl)azo]-3-(phenylazo)-2,7-naphthalene disulfonate (CI20470; Acid Black No. 1), chromium complex of 3-hydroxy-4-[(2-hydroxynaphth-1-yl) azo]-7-nitro-1-naphthalenesulfonic acid (3:2) (CI15711; Acid Black No. 52), disodium 3-[(2,4-dimethyl-5-sulfophenyl)azo]-4-hydroxy-1-naphthalene-sulfonate (CI14700; Food Red No. 1; Ponceau SX; FDandC Red No. 4), tetrasodium 4-(acetylamino)-5-hydroxy-6-[(7-sulfo-4-[(4-sulfophenyl)azo]naphth-1-yl)azo]-1,7-naphthalene disulfonate (CI28440; Food Black No. 1), chromium complex of sodium 3-hydroxy-4-(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazole-4-ylazo)-naphthalene-1-sulfonate (Acid Red No. 195).
The above-named nitro, azo, anthraquinone or triphenylmethane dyes, which are picked up directly, may be contained in a total amount of about 0.01 to 4% by weight, the total content of non-oxidative dyes preferably amounting to about 0.01 to 8% by weight and particularly to 0.1 to 5% by weight.
The inventive dye compositions based on compounds of the general formula (I), as well as optionally dyes, which are picked up directly, are preferably in the form of a solution, particularly an aqueous-alcoholic solution. Further preferred forms of compositions of the invention are creams, gels or emulsions. It is also possible to dispense these materials from a pressurized container with the help of an atomizer or different suitable pumping devices or spraying devices or in admixture with conventional, liquefied blowing agents under pressure as an aerosol spray or an aerosol foam.
The pH of the dye compositions according to the invention is within the range of 3 to 12 and particularly within the range of 8 to 11.5. Preferably, the pH is adjusted with ammonia to alkaline values. However, it can also be adjusted to such values with organic amines, such as monoethanolamine or triethanolamine. For adjustments to an acidic pH, diluted organic or inorganic acids, such as hydrochloric, sulfuric, phosphoric, ascorbic or lactic acid can be used, depending on the pH desired.
These dye compositions are used for dyeing hair in the usual manner by applying an amount of the dye composition, sufficient for the dyeing, on the hair, with which it remains in contact for a time, preferably 15 to 30 minutes. Subsequently, the hair is rinsed with water, then optionally with an aqueous solution of a weak organic acid and subsequently dried. As weak organic acid, acetic, citric or tartaric acid, for example, can be used in the form of a dilute aqueous solution.
The dye composition, which is described above and to which no oxidizing agent has been added, may furthermore contain natural or synthetic polymers or modified polymers of natural origin, which are customarily used for cosmetic materials. As a result, strenghthening of the hair is achieved simultaneously with the coloring. Such materials generally are feferred to as shade fortifier or color fortifier.
Of the synthetic polymers, known for this purpose in cosmetics, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylate compounds, such as polyacrylic acid or polymethacrylic acid, basic polymers of esters of polyacrylic acid, polymethacrylic acid and amino alcohols, for example, their salts or quatemization products, polyacrylonitrile, polyvinyl acetate and copolymers of such compounds, such as polyvinyl pyrrolidone-vinyl acetate are, for example, mentioned. As natural polymers or modified natural polymers, chitosan (deacetylated chitin) or chitosan derivatives may, for example, be used. The aforementioned polymers may be contained in the inventive materials in amounts, customary for such materials, especially in amounts of about 1 to 5% by weight. The pH of the inventive shade or color fortifier is about 6 to 9.
The hair dye composition according to the invention with additional strength is used in the known and conventional manner by moistening the hair with the fortifier, setting the hair for the hair style and subsequently drying.
Of course, the hair dye composition without oxidizing agent, described above, may optionally contain further additives, which are customary in hair dye compositions, such as care materials, wetting agents, thickeners, plasticizers, preservatives and perfume oils, as well as other conventional additives, listed below for oxidation hair dye compositions.
As already mentioned, hair dye compositions, for which the addition of an oxidizing agent is required, are also an object of the present invention. Aside from the dyes of the general formula (I), as well as, optionally, further dyes, which are picked up directly by the hair and comprise the group consisting of nitro, azo, anthraquinone and triphenylmethane dyes, these dye compositions additionally contain known oxidation dye precursors, which require an oxidative treatment (developer and coupler substances).
Examples of developers are 1,4-diamino-benzene (p-phenylenediamine), 1,4-diamino-2-methyl-benzene (p-toluylenediamine), 1,4-diamino-2,6-dimethyl-benzene, 1,4-diamino-2,5-dimethyl-benzene, 1,4-diamino-2,3-dimethyl-benzene, 2-chloro-1,4-diaminobenzene, 4-phenylamino-aniline, 4-dimethylamino-aniline, 4-diethylamino-aniline, 4-[di(2-hydroxyethyl)amino]-aniline, 4-[(2-methoxyethyl)amino]-aniline, 4-[(3-hydroxypropyl)amino]-aniline, 1,4-diainino-2-(2-hydroxyethyl)-benzene, 1,4-diamino-2-(1-methylethyl)-benzene, 1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol, 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, 4-amino-phenol, 4-amino-3-methyl-phenol, 4-methylamino-phenol, 4-amino-2-(aminomethyl)-phenol, 4-amino-2-[(2-hydroxyethyl)-amino]methyl-phenol, 4-amino-2-(methoxymethyl)-phenol, 4-amino-2-(2-hydroxyethyl)-phenol, 5-amino-salicylic acid, 2,5-diamino-pyridine, 2,4,5,6-tetraamino-pyrimidine, 2,5,6-triamino-4-(1H)-pyrimidone, 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole, 4,5-diamino-1-(1-methylethyl)-1H-pyrazole, 4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazole, 1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazole, 4,5-diamino-1-methyl-1H-pyrazole, 2-amino-phenol, 2-amino-6-methyl-phenol, 2-amino-5-methyl-phenol. The developer substances named can be used individually or also in admixture with one another.
Examples of couplers are 5-((2-hydroxyethyl)amino)-2-methoxyaniline, N-(3-dimethylamino-phenyl)-urea, 2,6-diamino-pyridine, 2-amino-4-[(2-hydroxyethyl)amino]-anisole, 2,4-diamino-1-fluoro-5-methyl-benzene, 2,4-diamino-1-methoxy-5-methyl-benzene, 2,4-diamino-1-ethoxy-5-methyl-benzene, 2,4-diamino-1-(2-hydroxyethoxy)-5-methyl-benzene, 2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxy-benzene, 2,3-diamino-6-methoxy-pyridine, 3-amino-6-methoxy-2-(methylamino)-pyridine, 2,6-diamino-3,5-dimethoxy-pyridine, 3,5-diamino-2,6-dimethoxy-pyridine, 1,3-diamino-benzene, 2,4-diamino-1-(2-hydroxyethoxy)-benzene, 2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene, 1-(2-aminoethoxy)-2,4-diamino-benzene, 2-amino-1-(2-hydroxyethoxy)-4-methylamino-benzene, 2,4-diaminophenoxy-acetic acid, 3-[di(2-hydroxyethyl)amino]-aniline, 4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxy-benzene, 5-methyl-2-(1-methylethyl)-phenol, 3-[(2-hydroxyethyl)amino]-aniline, 3-[(2-aminoethyl)amino]-aniline, 1,3-di(2,4-diaminophenoxy)-propane di(2,4-diaminophenoxy)-methane, 1,3-diamino-2,4-dimethoxy-benzene, 2,6-bis(2-hydroxyethyl)amino-toluene, 4-hydroxyindole, 3-dimethylamino-phenol, 3-diethylamino-phenol, 5-amino-2-methyl-phenol, 5-amino-4-fluoro-2-methyl-phenol, 5-amino-4-methoxy-2-methyl-phenol, 5-amino-4-ethoxy-2-methyl-phenol, 3-amino-2,4-dichloro-phenol, 5-amino-2,4-dichloro-phenol, 3-amino-2-methyl-phenol, 3-amino-2-chloro-6-methyl-phenol, 3-amino-phenol, 2-[(3-hydroxyphenyl)amino]-acetamide, 5-[(2-hydroxyethyl)amino]-2-methyl-phenol, 3-[(2-hydroxyethyl)amino]-phenol, 3-[(2-methoxyethyl)amino]-phenol, 5-amino-2-ethyl-phenol, 2-(4-amino-2-hydroxyphenoxy)-ethanol, 5-[(3-hydroxypropyl) amino]-2-methyl-phenol, 3-[(2,3-dihydroxypropyl)amino]-2-methyl-phenol, 3-[(2-hydroxyethyl)amino]-2-methyl-phenol, 2-amino-3-hydroxy-pyridine, 5-amino-4-chloro-2-methyl-phenol, 1-naphthol, 1,5-dihydroxy-naphthalene, 1,7-dihydroxy-naphthalene, 2,3-dihydroxy-naphthalene, 2,7-dihydroxy-naphthalene, 2-methyl-1-naphthol-acetate, 1,3-dihydroxy-benzene, 1-chloro-2,4-dihydroxy-benzene, 2-chloro-1,3-dihydroxy-benzene, 1,2-dichloro-3,5-dihydroxy-4-methyl-benzene, 1,5-dichloro-2,4-dihydroxy-benzene, 1,3-dihydroxy-2-methyl-benzene, 3,4-methylenedioxy-phenol, 3,4-methylenedioxy-aniline, 5-[(2-hydroxyethyl)amino]-1,3-benzodioxol, 6-bromo-1-hydroxy-3,4-methylenedioxy-benzene, 3,4-diamino-benzoic acid, 3,4-dihydro-6-hydroxy-1,4-(2H)-benzoxazine, 6-amino-3,4-dihydro-1,4(2H)-benzoxazine, 3-methyl-1-phenyl-5-pyrazolone, 5,6-dihydroxy-indole, 5,6-dihydroxy-indolin, 5-hydroxy-indole, 6-hydroxy-indole, 7-hydroxy-indole, 2,3-indolindione. The coupler substances named can be used individually as well as in admixture with one another.
As particularly preferred compounds, especially 1,4-diamino-2-methyl-benzene, 4-[(di(2-hydroxyethyl)amino]-aniline, 1,4-diamino-2-(2-hydroxyethyl)-benzene, 4-amino-3-methylphenol, 4-amino-2-(aminomethyl)-phenol, 2,4,5,6-tetraaminopyrimidine, 4,5-diamino-1-(2-hydroxy-ethyl)-1H-pyrazole, 4-chlororesorcinol, 3-aminophenol, 5-hydroxy-1,3-benzodioxol, 5-amino-1,3-benzodioxol, 5-((2xe2x80x2-hydroxyethyl)-amino)-1,3-benzodioxol, 2-amino-4-[(2-hydroxyethyl)amino]-anisole, 2,4-diamino-1-fluoro-5-methyl-benzene, 5-amino-2-methylphenol, 1,3-di(2,4-diaminophenoxy)-propane, 3-amino-2-chloro-6-methyl-phenol, 1-naphthol, 1,3-dihydroxy-benzene, 1,3-dihydroxy-2-methyl-benzene, 2,4-diamino-1-(2-hydroxyethoxy)-benzene, 5-((2-hydroxyethyl)amino)-2-methoxyaniline and 5-((3-hydroxypropyl)amino)-2-methylphenol, come into consideration.
Further oxidation dyes, known and used for coloring hair, are described, for example, in the book by E. Sagarin, xe2x80x9cCosmetics, Science and Technologyxe2x80x9d (1957), Interscience Publishers Inc., New York, pages 503 ff, as well as in the book by H. Janistyn, xe2x80x9cHandbuch der Kosmetika und Riechstoffe (Handbook of Cosmetics and Fragrances), volume 3xe2x80x9d (1973), pages 388 to 397.
Very good natural blonde and brown shades as well as fashionable nuances can be produced with combinations of oxidation dyes and the dyes of formula (I).
The inventive dyes of formula (I) are contained in the coloring agents, to which an oxidation agent has been added, preferably in an amount of 0.01 to 4.0% by weight and especially of 0.02 to 2.0% by weight, the total content of non-oxidative dyes preferably amounting to about 0.1 to 5% by weight.
The total concentration of oxidation dye precursor in the inventive oxidation coloring agent is between about 0.1 and 10% by weight, an amount of 0.2 to 2% by weight being preferred.
The pH of the oxidation dye composition can be adjusted to an acidic, a neutral or a basic value (pH=3 to 12), a pH of 6 to 12 and particularly a pH of about 8.0 to 11.5 being preferred. The pH is adjusted to the desired alkaline value usually by ammonia; however, other organic amines, such as monoethanolamine or triethanolamine or inorganic bases, such as sodium hydroxide and potassium hydroxide, can also be used. The pH is adjusted to an acidic value with organic acids, such as citric, glycolic, lactic, malic, ascorbic or tartaric acid.
As oxidation agent for developing the coloration, primarily hydrogen peroxide and its addition compounds come into consideration. The inventive oxidation dye composition may be prepared in a form, which is identical to that of the inventive non-oxidative dye composition, the oxidation dye composition preferably being in the form of a cream or a gel.
Conventional additives in solutions, creams, emulsions or gels are, for example, solvents such as water, lower molecular weight aliphatic monohydric or multihydric alcohols, their esters and ethers, such as alkanols, particularly with 1 to 4 carbon atoms, such as ethanol, propanol or isopropanol, butanol, isobutanol, dihydric and trihydric alcohols, especially those with 2 to 6 carbon atoms, such as ethylene glycol, propylene glycol, 1,3-dihydroxypropane, 1,4-dihydroxybutane, 1,5-dihydroxypentane, 1,6-dihydroxyhexane, 1,2,6-trihydroxyhexane, glycerin, diethylene glycol, dipropylene glycol, polyalkylene glycols, such as triethylene glycol, polyethylene glycol, tripropylene glycol, polypropylene glycol, lower molecular weight alkyl ethers of multihydric alcohols, such as ethylene glycol monomethyl ether or ethylene glycol monoethyl ether or ethylene glycol monopropyl ether or ethylene glycol monobutyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether, triethylene glycol monomethyl ether or triethylene glycol monoethyl ether, ketones and keto alcohols, particularly those with 3 to 7 carbon atoms, such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl phenyl ketone, cyclopentanone, cyclohexanone and diacetone alcohol, ethers, such as dibutyl ether, tetrahydrofiran, dioxane, diisopropyl ether, esters, such as ethyl formate, methyl formate, methyl acetate, ethyl acetate, propylene acetate, butyl acetate, phenyl acetate ethylene glycol monoethyl ether acetate and hydroxyethyl acetate, amides, such as dimethylformamide and dimethylacetamide, N-methylpyrrolidone as well as urea, tetramethylurea and thiodiglycol.
Furthermore, the inventive dye compositions may contain wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric, nonionic or zwitterionic surface active substances, such as fatty alcohol sulfates, alkanesulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkylbetaines, xcex1-olefinsulfonates, ethoxylated fatty alcohols, ethoxylated nonyiphenols, fatty acid alkanolamines, ethoxylated fatty esters, fatty alcohol polyglycol ether sulfates, alkyl polyglucosides, thickening agents, such as higher molecular weight fatty alcohols, starch, algenates, bentonites, cellulose derivatives, Vaseline, paraffin oil and fatty acids, water-soluble polymeric thickening agents, such as natural types of gum, guar gum, xanthan gum, carob core flour, pectin, dextran, agar, amylose, amylopectin, dextrins, clays or fully synthetic hydrocolloids, such as polyvinyl alcohol, as well as care materials, such as lanolin derivatives, cholesterol, pantothenic acid, water soluble cationic polymers, protein derivatives, provitamins, vitamins, plant extracts, sugar and betaine, auxiliary materials, such as moisturizers, electrolytes, antioxidants, fatty amides, sequestering agents, film-forming agents and preservatives. Aside from water, a water-soluble organic solvent or a mixture of such solvents, as well as a water/solvent mixture may also be used.
The components mentioned are used in amounts customary for such purposes. For example, the wetting agents and emulsifiers are used in concentrations of about 0.5 to 30% by weight, the thickeners in an amount of about 0.1 to 25% by weight and the care materials in an amount of about 0.1 to 5% by weight.
When used for the oxidative coloring of hair, the dye composition, described above, is mixed immediately before use with an oxidizing agent and an amount, sufficient for the hair coloring treatment and depending on the thickness of the hair, generally from 60 to 200 g of this mixture, is applied to the hair. As oxidizing agent for developing the hair coloring, mainly hydrogen peroxide or its addition compounds with urea, melamine or sodium borate come into consideration in the form of 3% to 12% and preferably 6% aqueous solutions.
If a 6% hydrogen peroxide solution is used as oxidizing agent, the ratio by weight of dye composition to oxidizing agent is 5:1 to 1:2 and preferably 1:1. Larger amounts of oxidizing agent are used especially when the dye concentrations in the dye composition are higher or if a strong bleaching of the hair is intended at the same time.
The dye solution is allowed to act on the hair at 20xc2x0 to 50xc2x0 C. for about 10 to 45 minutes and preferably at 40xc2x0 C. for 40 minutes. The hair is then rinsed with water and dried. Optionally, at the conclusion of the rinsing, the hair is washed with a shampoo, rinsed and subsequently dried.
Especially when coloring hair, the dye composition according to the invention leads to dyed colors with excellent fastness properties, especially with respect to light fastness, wash fastness and perspiration fastness. The high color intensity and the purity of the color of the achievable colorations are remarkable even after a three-month storage. Finally, gray hair, which has not been damaged chemically, can also be tinted without problems and with good covering power with the dye composition described. Independently of the different structure of the hair, the colorations obtained are uniform and well reproducible. Depending on their composition, the dye compositions are used either in conjunction with and also without an oxidizing agent.
The dye compositions according to the invention, based on compounds of formula (I), are suitable particularly for dyeing keratin fibers, such as wool, furs or hair, especially human hair. It is, however, also readily possible to dye other natural fibers such as cotton, jute, sisal, linen or silk, modified natural fibers such as regenerated cellulose, nitrocellulose, alkylcellulose, hydroxyalkylcellulose or acetylcellulose, or synthetic fibers, such as polyamide fibers, polyurethane fibers and polyester fibers with these dye compositions.